CN113929881A - Preparation method for synthesizing conjugated photoelectric polymer based on continuous flow microreactor - Google Patents
Preparation method for synthesizing conjugated photoelectric polymer based on continuous flow microreactor Download PDFInfo
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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Abstract
The invention discloses a preparation method for synthesizing a conjugated photoelectric polymer based on a continuous flow microreactor, and relates to the field of polymer synthesis. The continuous flow micro-reactor comprises a liquid storage tank (1), a high-pressure constant flow pump (2), a micro-reaction channel (3), a heating system (4) and a product tank (5); the preparation method specifically comprises the following steps: after raw material liquid is obtained in a liquid storage tank (1) in a configuration mode, setting flow rate parameters of a constant flow pump (2) and starting the constant flow pump (2), so that the raw material liquid enters a micro-reaction channel (3) at a set flow rate and is subjected to polymerization reaction in the channel (3), wherein before the raw material liquid enters the micro-reaction channel (3), the micro-reaction channel (3) is heated by a heating system (4) to reach a required reaction temperature, and a polymerization reaction product passing through the micro-reaction channel (3) directly flows into a product tank (5). The method provided by the invention has the advantages of high reaction speed, accurate and controllable steps, good repeatability, simple and efficient operation and easiness in mass production amplification.
Description
Technical Field
The invention relates to the field of polymer synthesis, in particular to a preparation method for synthesizing a conjugated photoelectric polymer based on a continuous flow microreactor.
Background
Compared with the traditional inorganic semiconductor, the photoelectric conjugated polymer not only has the electronic characteristic of metal or semiconductor, but also has excellent processing characteristic and mechanical property of the polymer, and can be used for preparing large-area flexible photoelectronic devices in a low-temperature solution processing mode. Due to these unique advantages, the research of photoelectric polymer has attracted the extensive attention of academic circles and industrial circles at home and abroad, and the photoelectric polymer material and the application thereof in the related photoelectric devices have been rapidly developed. For example, the light efficiency of the white light polymer light emitting diode is 50lm/W higher, and the efficiency level of a fluorescent lamp is reached; field effect transistors based on photo-voltaic polymers have surpassed the device performance of amorphous silicon; the photoelectric conversion efficiency of the high-molecular photovoltaic device exceeds 18 percent, and the photoelectric high-molecular material shows huge commercial application prospect.
Nowadays, the synthesis method of conjugated photoelectric polymers mainly comprises cross-coupling reactions of Suzuki, Stille, Sonogashira and the like, namely, a polymerization reaction of a bisstannide monomer A and a bisbromide monomer B under a metal catalyst.
Although the chemical synthesis of the conjugated polymer is becoming more sophisticated, there is still a large gap in the control of the structure compared to the conventional polymer. At present, the synthesis of the conjugated photoelectric polymer still remains in the traditional bottle type or kettle type reaction, and the reaction mainly has the following defects:
(1) uneven heat transfer: because the heat exchange between the oil bath and the reaction is limited by the flask, the reaction temperature close to the flask is different from the internal environment of the reaction liquid, so that the whole polymerization reaction has different reaction environments, and the uniformity of polymerization is influenced;
(2) poor repeatability, low efficiency: since the reaction requires human operations from the initial charge to the final stop, operational errors are inevitably introduced during the reaction, affecting the reproducibility of the product, and the reproducibility based on this system is poor, resulting in the need to synthesize the material "in small numbers and many times", with low efficiency;
(3) the amplification effect is severe: in the amplification reaction based on the reaction flask, because the reaction environments such as heat transfer area, stirring rate and the like cannot be amplified in a same proportion, an obvious amplification effect can be generated;
(4) the reaction time is too long and the yield is low: typically, several hours are required for the reaction to take place once.
Therefore, in the conventional bottle-type or tank-type system, the repeatability of the synthesis of the conjugated polymer material is problematic, wherein the repeatability mainly includes the molecular weight and distribution controllability, the structure (including terminal group, conformation/configuration isomerism, and the like) defects of the conjugated polymer, and the bottle-type or tank-type reaction also has a serious amplification effect. Therefore, even though the photoelectric conjugated polymer has made great progress in the application of new energy materials, the photoelectric conjugated polymer has a certain distance from the practical large-scale application.
Disclosure of Invention
In view of the above defects in the prior art, the technical problem to be solved by the present invention is to provide a method for synthesizing a photoelectric conjugated polymer by using a continuous flow reactor, so as to achieve the effects of fast reaction speed, accurate and controllable reaction steps, good repeatability, simple and efficient operation, and easy amplification of mass production.
In order to achieve the above object, the present invention provides a method for synthesizing a conjugated photoelectric polymer based on a continuous-flow microreactor, which comprises:
a liquid storage tank (1) for storing a raw material liquid,
a high-pressure constant flow pump (2) which is connected with the liquid storage tank (1) through a pipeline and is used for controlling the flow rate of the raw material liquid,
a micro-reaction channel (3) which is connected with the constant flow pump (2) through a pipeline and is a place where polymerization reaction occurs,
a heating system (4) for heating the micro reaction channel (3),
a product tank (5) connected to the micro reaction channel (3) through a pipe for receiving a polymerization reaction product;
the method comprises the following steps:
and 4, enabling the polymerization reaction product to flow out of the micro reaction channel (3) and then enter the product tank (5), so that the polymerization reaction product is collected.
In some embodiments, the molar ratio of the bis-tin conjugated compound monomer to the bis-bromine conjugated compound monomer is 1: 1.
In some embodiments, the bistin-conjugated compound monomer is (4, 8-bis (5- (2-ethylhexyl) -4-fluorothienyl) benzo [1,2-B:4,5-B '] dithienyl) bistrimethyltin and the bisbromo-conjugated compound monomer is 1, 3-bis (5-bromothiophene) -5, 7-bis (2-isooctyl) benzo [1,2-c:4, 5-c' ] dithiophene-4, 8-dione.
In some embodiments, the organic solvent is toluene, xylene, chlorobenzene, or any combination thereof.
In some embodiments, the catalyst is tetrakistriphenylphosphine palladium, palladium bis (dibenzylideneacetone), palladium dichloride, o-methyltriphenylphosphine, or any combination thereof.
In some embodiments, the flow rate parameter of the high-pressure constant-flow pump (2) is set to be 2-10 mL/min, preferably 7-9 mL/min.
In some embodiments, the temperature of the heating system (4) is set at 100-.
In some embodiments, the product tank (5) contains a poor solvent that is a mixture of hydrochloric acid and a polar organic solvent that is methanol, ethanol, acetone, or any combination thereof. The polymerization reaction product flows into a product tank containing poor solvent to generate precipitation reaction, and the dried conjugated photoelectric polymer product can be obtained after filtering and drying.
In some embodiments, the mass ratio of the hydrochloric acid to the polar organic solution in the mixed solution of the hydrochloric acid and the polar organic solution is 2 to 10 wt%.
In some embodiments, the micro reaction channel (3) is helical.
In some embodiments, the micro-reaction channel (3) has a radius of 0.5mm and a length of 100 m.
Compared with the prior art, the invention has the following beneficial effects:
(1) because the continuous flow reactor has high manufacturing cost, and a commercial synthesizer suitable for synthesizing the photoelectric conjugated polymer does not exist at present, and considering the commercial application prospect of the future photoelectric conjugated polymer, the invention is based on the continuous flow technology, and independently builds the micro-reaction synthesizer suitable for synthesizing the photoelectric conjugated polymer material, can realize the continuous production of the photoelectric conjugated polymer, and realizes the controllable synthesis (controllable molecular weight and uniform distribution), high yield (more than 90 percent), good repeatability and large-scale industrial application by repeatedly testing the reaction conditions (molar ratio, temperature, flow rate, micro-reaction channel radius and the like);
(2) the photoelectric conjugated polymer material prepared by the continuous flow reactor has no amplification effect, and no matter gram-level or kilogram-level yield is realized, the number of the continuous flow reactors and/or the amount of raw material liquid only need to be increased, and the risk from a small test to a large test of reaction does not need to be considered;
(3) the reaction time for synthesizing the conjugated polymer is shortened to within one hour from tens of hours of the traditional reaction time, so that the reaction efficiency is obviously improved, and the productivity of the polymer is favorably improved;
(4) the spiral micro-reaction channel is utilized, the specific surface is larger for heat transfer, and compared with the traditional kettle type reactor, the uniformity of the reaction environment and the purity of the product are obviously improved;
(5) the post-treatment mode is to directly flow the polymerization reaction product into a poor solvent for sedimentation, directly separate out a solid product, and then obtain a required product by filtering and drying, thereby simplifying the original complex and fussy manual treatment mode, obviously optimizing the process flow and reducing the cost.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a schematic diagram of a continuous-flow microreactor in accordance with a preferred embodiment of the present invention;
wherein: 1-a liquid storage tank, 2-a high-pressure constant flow pump, 3-a micro-reaction channel, 4-a heating system and 5-a product tank.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
In the drawings, structurally identical elements are represented by like reference numerals, and structurally or functionally similar elements are represented by like reference numerals throughout the several views. The size and thickness of each component shown in the drawings are arbitrarily illustrated, and the present invention is not limited to the size and thickness of each component. The thickness of the components may be exaggerated where appropriate in the figures to improve clarity.
As shown in FIG. 1, the continuous-flow microreactor mainly comprises a liquid storage tank 1, a high-pressure constant-flow pump 2, a microreaction channel 3, a heating system 4, and a product tank 5.
The liquid storage tank 1 is used for storing raw material liquid, an opening can be arranged at the upper part of the liquid storage tank 1, and raw materials are directly added into the liquid storage tank 1 through the opening. The liquid storage tank 1 is also provided with a stirring device, so that the solid raw materials are completely dissolved and are uniformly mixed with the liquid raw materials.
The high-pressure constant flow pump 2 is connected with the liquid storage tank 1 through a pipeline, the constant flow pump 2 can convey the raw material liquid from the liquid storage tank 1 to the micro-reaction channel 3, and the flow rate of the raw material liquid is controlled.
The micro-reaction channel 3 is a place where polymerization reaction occurs, is spiral, has a radius of 0.5mm and a length of 100m, and the micro-reaction channel 3 needs to be preheated to reach a required temperature before a raw material liquid passes through the micro-reaction channel 3.
The heating system 4 serves to heat the micro reaction channel 3 and maintain the micro reaction channel 3 at a constant temperature.
The product tank 5 is connected with the micro reaction channel 3 through a pipeline, and the reaction product after passing through the micro reaction channel 3 directly flows into the product tank 5. The product tank 5 can be filled with a poor solvent, so that the polymerization reaction product is directly precipitated in the product tank 5, and the precipitate is filtered and dried to obtain a dry target product.
Example 1
The embodiment provides a method for synthesizing a polymer photoelectric material PM6 by using a continuous flow reactor, which comprises the following steps:
and 4, allowing the polymerization reaction product to flow out of the micro reaction channel 3 and then enter a product tank 5, wherein the product tank 5 is filled with a mixed solution of 250ml of concentrated hydrochloric acid and 3L of ethanol, the polymerization reaction product is subjected to precipitation reaction in a receiving tank 5, and the polymer photoelectric material PM6 can be obtained after filtering and drying.
The final product was calculated to be about 20.5g with a yield of 93.6%. The molecular weight Mn was found to be 30,343Da and the PDI was found to be 2.3, indicating a relatively uniform molecular weight distribution. The photoelectric conversion efficiency of an organic solar device prepared by taking the polymer photoelectric material PM6 as a donor is 15.3%.
Example 2
The embodiment provides a method for synthesizing a polymer photoelectric material PM6 by using a continuous flow reactor, which comprises the following steps:
and 4, allowing the polymerization reaction product to flow out of the micro reaction channel 3 and then enter a product tank 5, wherein the product tank 5 is filled with a mixed solution of 250ml of concentrated hydrochloric acid and 3L of ethanol, the polymerization reaction product is subjected to precipitation reaction in a receiving tank 5, and the polymer photoelectric material PM6 can be obtained after filtering and drying.
The final calculated product was about 20.6g, with a yield of 93.8%. The molecular weight Mn was found to be 33,100Da and the PDI was found to be 2.27, indicating a relatively uniform molecular weight distribution. The photoelectric conversion efficiency of an organic solar device prepared by taking the polymer photoelectric material PM6 as a donor is 15.8%.
Example 3
The embodiment provides a method for synthesizing a polymer photoelectric material PM6 by using a continuous flow reactor, which comprises the following steps:
and 4, allowing the polymerization reaction product to flow out of the micro reaction channel 3 and then enter a product tank 5, wherein the product tank 5 is filled with a mixed solution of 250ml of concentrated hydrochloric acid and 3L of ethanol, the polymerization reaction product is subjected to precipitation reaction in a receiving tank 5, and the polymer photoelectric material PM6 can be obtained after filtering and drying.
The final product was calculated to be about 20.7g with a yield of 94.2%. The molecular weight Mn was found to be 36,900Da and the PDI was found to be 1.9, indicating a relatively uniform molecular weight distribution. The organic solar device prepared by taking the polymer photoelectric material PM6 as a donor has the photoelectric conversion efficiency of 16.7 percent, meets the requirement of commercial quality, and can be effectively applied to the field of photoelectric conversion.
Comparative example 1
Comparative example a conventional kettle reaction was used to synthesize a polymeric photovoltaic material PM6, comprising the steps of:
and 2, deoxidizing the reaction flask filled with the reaction liquid.
And 3, placing the reaction flask containing the reaction solution in an oil bath at 110 ℃ for reaction.
And 4, after the reaction is carried out for 8 hours, stopping the reaction, pouring the reaction liquid into ethanol for sedimentation, filtering and drying to obtain the polymer photoelectric material PM 6.
The final product was calculated to be about 19.4g, 88.6% yield. The molecular weight Mn was found to be 28,500Da and the PDI was found to be 2.3. The photoelectric conversion efficiency of an organic solar device prepared by taking the polymer photoelectric material PM6 as a donor is 14.3%. The reaction progress is reduced and the material performance is obviously reduced when the traditional condition is amplified to gram level.
Comparative example 2
Comparative example a conventional kettle reaction was used to synthesize a polymeric photovoltaic material PM6, comprising the steps of:
and 2, deoxidizing the reaction flask filled with the reaction liquid.
And 3, placing the reaction flask containing the reaction solution in an oil bath at 110 ℃ for reaction.
Under the reaction condition, when the reaction is carried out for 10min, the reaction solution is rapidly converted into gel from mucus, namely, the molecular weight is rapidly increased, and the solubility is rapidly reduced, so that the method is not suitable for preparing solar devices. Therefore, the reaction conditions are severe and not conducive to manual operation.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. A preparation method for synthesizing a conjugated photoelectric polymer based on a continuous-flow microreactor is characterized in that the continuous-flow microreactor comprises:
a liquid storage tank (1) for storing a raw material liquid,
a high-pressure constant flow pump (2) which is connected with the liquid storage tank (1) through a pipeline and is used for controlling the flow rate of the raw material liquid,
a micro-reaction channel (3) which is connected with the constant flow pump (2) through a pipeline and is a place where polymerization reaction occurs,
a heating system (4) for heating the micro reaction channel (3),
a product tank (5) connected to the micro reaction channel (3) through a pipe for receiving a polymerization reaction product;
the method comprises the following steps:
step 1, adding an organic solvent into the liquid storage tank (1), adding a polymerization monomer and a catalyst into the organic solvent, and stirring and dissolving to obtain a raw material liquid; the polymerization monomer comprises a double-tin conjugated compound monomer and a double-bromine conjugated compound monomer;
step 2, setting the temperature of the heating system (4) and starting the heating system (4) to enable the micro-reaction channel (3) to be at a preset temperature and keep the temperature constant;
step 3, setting flow rate parameters of the constant flow pump (2) and starting the constant flow pump (2) to enable the raw material liquid to enter the micro-reaction channel (3) at the set flow rate and to generate a polymerization reaction in the micro-reaction channel (3);
and 4, enabling the polymerization reaction product to flow out of the micro reaction channel (3) and then enter the product tank (5), so that the polymerization reaction product is collected.
2. The method for preparing a conjugated photoelectric polymer by continuous-flow microreactor-based synthesis according to claim 1, wherein the molar ratio of the bis-tin conjugated compound monomer to the bis-bromine conjugated compound monomer is 1: 1.
3. The method according to claim 1, wherein the monomer of the bis-tin conjugated compound is (4, 8-bis (5- (2-ethylhexyl) -4-fluorothienyl) benzo [1,2-B:4,5-B '] dithienyl) bistrimethyltin, and the monomer of the bis-bromine conjugated compound is 1, 3-bis (5-bromothiophene) -5, 7-bis (2-isooctyl) benzo [1,2-c:4, 5-c' ] dithiophene-4, 8-dione.
4. The method according to claim 1, wherein the organic solvent is toluene, xylene, chlorobenzene or any combination thereof.
5. The method according to claim 1, wherein the catalyst is palladium tetrakistriphenylphosphine, palladium bis (dibenzylideneacetone), palladium dichloride, o-methyltriphenylphosphine, or any combination thereof.
6. The preparation method for synthesizing the conjugated photoelectric polymer based on the continuous-flow microreactor according to claim 1, wherein the flow rate parameter of the constant-flow pump (2) is set to be 2-10 mL/min.
7. The method for preparing the conjugated photoelectric polymer based on the continuous-flow microreactor-based synthesis according to claim 1, wherein the temperature of the heating system (4) is set to 100-140 ℃.
8. The method for preparing the conjugated photoelectric polymer based on continuous-flow microreactor synthesis according to claim 1, wherein the product tank (5) contains a poor solvent, the poor solvent is a mixed solvent of hydrochloric acid and a polar organic solvent, and the polar organic solvent is methanol, ethanol, acetone or any combination thereof.
9. The method according to claim 8, wherein the mass ratio of the hydrochloric acid to the polar organic solution in the mixed solution of hydrochloric acid and a polar organic solution is 2-10 wt%.
10. The method for preparing a conjugated photoelectric polymer based on continuous-flow microreactor synthesis according to claim 1, wherein the micro-reaction channel (3) is helical; the radius of the micro-reaction channel (3) is 0.5mm, and the length is 100 m.
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